Process for the synthetic production of titanium-nitrogen compounds



' sin? and Joint F.

UNITED STATES FOORD VON BICHOWSKY AND JOHN F. HARTKAN.

PATENT OFFICE.

OF POMONA, CALIFORNIA.

No Drawing.

To all 'whom it may concern.

Be it known that we, Foonn voN Bic-now- HARTHAN, both citizens of the United States. residing at Pomona, in the county of Los Angeles and State of California, have invented a new and useful Process for the Synthetic Production of Titanium- Nitrogen Compounds, of which the following is a specification.

his invention relates to the synthetic production of titanium-nitrogen compounds (un operations.

der which term we include the nitrid T1 3 and the, so-called cyanonitrid Ti(( N),. Ti ,N of titanium, or a mixture of these compounds) by the reaction of nitrogen and hydrocarbon gases or vapors inthe presence of a catalytic agent. It is known that nitrogen gas will combine with suitable compounds of titanium at a lower temperature and more rapidly when the reaction takes place in the presence of an alkali metal salt than if such salt is not present. e have discovered that if the catalytic agent contains a metal of the iron group, as well as the alkali metal salt, the reaction can be effected more expeditiously at a still lower temperature. e have also discovered that by employing a hydrocarbon gas or vapor with the nitrogen the catalytic reactive mass employed may be prepared free of carbon. It is to be understood that the term hydrocarbon gas employed in this specification has a generic meaning and that it defines all forms of natural gas, whether marsh or petroleum or any natural gases of the parafiin series which are, as is well known, simply impure forms of methane. The term hydrocarbon gas also defines any artificially prepared gas containing appreciable quantities of methane or its homogeners.

In general, this process consists in preparing the reacting gas by mixing together nitrogen and natural gas, or the gaseous vapor of suitable hydrocarbons, then passing the mixture of gases through the catalytic reactive mass at suitable temperatures for securing the desired reaction, an finally recovering from the catalytic reactive mass the titanium-nitrogen compounds.

The hydrocarbon employed may be any simple, easily volatilized hydrocarbon free from combined nitrogen such, for example, as benzol C H or a mixture of non-aromatic hydrocarbons such, for example, as gasolene or kerosene; or even the finely Specification of Letters latent.

Application filed June 1, 1920.

might contain and Patented Sept. 20, 1921 Serial No. 385,562.

atomized particles of crude oil or melted naphthalene C H In practice we use at mospheric nitrogen, by simply mixing air with impure methane or natural gas and then pass the mixture of gases over iron heated to a temperature of about 700 C. and we remove the resulting carbon dioxid in any suitable manner, for example, by absorption in water under pressure, or by passing through lime towers or by both of these This preliminary mixture of air and gas tends to decompose and thus remove any sulfur compounds which the gas the presence of which would be injurious to the catalytic mass as will be made clear hereinafter. This preliminary mixture of air and natural gas must be maintained at approximately the temperature stated, otherwise an excess of carbon might be split off and lost during the heating. The flow of mixed gas and air should be so regulated and the number of treatments so arranged that all of the oxygen in the air is removed in a combined form. The proportion of nitrogen used with the methane may vary, but in practice we at present find a mixture of two parts by volume of natural gas to one of air to be best, since in a mixture of such proportions the necessary amount of carbon is given off when the mixture is decomposed by the reactive mass at the comparatively high temperature employed.

The. catalytic reactive mass discovered by us to best suit the purpose comprises a mixture containing a suitable alkali or alkali metal salt, a suitable titanium compound, and a metal of the, so-called, iron group. The alkali may be, for example, the oxid or carbonate of sodium or the oxid or carbonate of potassium. The titanium compound may be any of the natural or artificially prepared oxids or mixed oxids. We prefer, however, to use the dioxid TiO or its naturally occurring, common form, the mineral known as rutile. The metal may be iron, nickel, or cobalt, or mixtures of any two of the same or all; and the metal may be either in the metallic form or in combination such as the oxids or carbonates.

When the reactive mass contains only the titanium compound, such as the dioxid, we find that the mass must be heated to a temperature of about 1500 C. before the nitrogen in the mixtu e 01 gases will react. We

also find that even when an alkali metal salt h is added the reaction does not begin until a meta used will be somewhat lowered because temperature of about 1100 is reached. of its absorption of carbon from the decomlowever, upon the addition of a metal or posed gases.

5 metals of the iron group the temperature at After the reaction 1s completed the n 1- which the reaction takes place'is materially trids will be recovered from the catalytlc lower, a rapid absorption and combination r activ mass. We ha've discovered that of the nitrogen and the titanium oxid taking thi an b d ne b rindin nd separating place at a. temperature of about 1000 C. In th h t li ht n trog n o und in view of this the process assumes commercial and undecomposed rutile from the heav1er value and is. technically, much easier to peri nd th r t lli rti l ithe by form than when a metal of the iron group is m ti ttr ti n, b hani al la sinot used. It makes but slight difference fication, by flotation or by a combination of whether the metal be originally present in any t or mor of these operations.

15 the metallic state orin some form of chemi- Th in-id or it id or i t cal combination. thereof thus obtained will then be decom Prefer to p y the alkali metal posed by superheated steam at a temperasalt a comparatively cheap carbonate such, t f h 00 (1 t lib t h d 20 fates or sulfids were used they would by -b d b th use f it bl r t If tcrrates are also useful salts in the process l t f t; as id id nd m onia as they llberate some sodium. either as the ld f r metal or the carbonate, upon reduction at the In order to make clear the process as We temperatures employed in this process. In h t ll d it a n r t xampl i all of the reactions the presence of carbon, i i as f ll Th eatalyzer i first r IW as such, in the catalyzer is not essential to pared by making a mixture of finely ground 9 the process, for the reason, hereinbefore t i l i proportions b i ht as f lmentioned, that the methane or other hydrol w carbon employed is ltself asource of sup- 7 ply of carbon for maintaining a reducing Titanium dioxid (rutile 35 medium or for supplying carbon to the pure) ,40parts. 1 cyanonitrid or for both of these. In p Sodium carbonate anhydrous 10 parts. paring the catalytic mass the lntroductlon Metallic iron 50 parts.

fitfor an entirely different reason, namely This mixture is then moistened with water 40 that such carbon compounds upon heating containing a small amount f a uitable decompose and thus liberate gases and steam binder such, for example, as lucose or mo- 45 tact for the gas. This action of the carbon briquets are then placed in upright or in- 1 in its compounds would not be, however, a clined retorts and heated to a temperature primary one. of about 900 C. or higher, air being exe temperature under which the reaction eluded by passing natural gas free from takes place may vary considerably within oxygen through the retorts while the 50 certain limitations. In this class of synthetic briquets are being heated. When a tempera- 11 processes the temperatures required are comture of about 900 C. is reached a mixture of paratively high and, without meaning to pure nitrogen, obtained from air, and natlimit the invention thereto, it may be stated ural gas, as hereinbefore described, is adthat we have discovered that a minimum mitted under slight pressure to the retorts 55 temperature of about 900 C. is required to or, if preferred, pure nitrogen carbureted bring about the reaction, the percentage of by mixing with a suitable hydrocarbon such combined nitrogen appearing to rise with for example, as crude oil distillate will be the temperature. There is naturally a maxiadmitted to the retorts. The hydrogen, mum temperature and such, in practice, is which is liberated by cracking or splitting 60 just below the melting point of whatever up of the methane, also has a strong reduc- 12 the reaction mass, thus stopping the passage to obtain the t st results the iron must be 66 of the gas through said mass. It may be finely divided .id for that reason we prefer to use the iron in the form of very fine filings.

The titanium dioxid formed by the decomposition of the nitrid or cyanonitrid with steam, as rep-resented by the equationand the metal recovered, as hereinbefore described, are mixed with the proper proportion of sodium carbonate and then worked into a fresh catalytic reactive mass in the form of briquets.

\Ve claim:

1. The process for the synthetic production of titanium-nitrogen compounds, which consists in passing a mixture of nitrogen and hydrocarbon gases or vapors through a heated catalytic reactive mass containing an oxygen-containing titanium compound, and then recovering the resulting titanium-nitrogen compound.

2. The process for the synthetic production of titanium-nitrogen compounds, which consists in passing a mixture of nitrogen and hydrocarbon gases or vapors through a heated catalytic reactive mass containing an oxygen-containing titanium compound, an alkaline substance and a metal of the iron group, and then recovering the resulting titanium-nitrogen compound. v

3. The process for the synthetic production of titanium-nitrogen compounds, which consists in passing a mixture of nitrogen and hydrocarbon gases or vapors through a heated catalytic reactive mass devoid of carbon and containing an oxygen-containing titanium compound, and then recovering the resulting titanium-nitrogen compound.

4. The process for the synthetic production of titanium-nitrogen compounds which consists in passing a mixture of nitrogen and hydrocarbon gases or vapors through a heated catalytic reactive mass devoid of car- .bon and containing an oxygen-containing titanium compound, an alkaline substance and a metal of the iron group, and then recovering the resulting titanium-nitrogen' compound.

5. The process for the synthetic production of titanium-nitrogen compounds, which consists in passing a mixture of nitrogen and hydrocarbon gases or vapors through a catalytic reactive mass heated to a temperature of approximately 1000 C. and containing an oxygen-containing titanium compound, and then recovering the resulting titaniumnitrogen compound.

6. The process for the synthetic production of titanium-nitrogen compounds, which consists in passing a mixture of nitrogen and hydrocarbon gases or vapors through a catalytic reactive mass heated to a temperature of approximately 1000 C. and containing an oxygen-containing compound, an alkaline substance and a metal of the iron group, and then recovering the resulting titanium-nitrogen compound.

7. In the process for the synthetic production of titanium-nitrogen compounds by catalysis, that step which consists in subjecting a mixture of nitrogen and hydrocarbon gases or vapors under a temperature of approximately 1000 C. to the action of a catalytic reactive mass, substantially devoid of carbon and comprising an oxygen-containing titanium compound capable of reacting with the nitrogen to produce a titanium-nitrogen compound.

8. The process for the synthetic production of titanium-nitrogen compounds, which consists in heating an oxygen-containing titanium compound in the presence of nitrogen and a hydrocarbon gas or vapor, and then recovering the resulting titanium-notrogen compound.

9. The process for the synthetic production of titanium-nitrogen compounds, which consists in heating an oxygen-containing titanium compound, carbon, an alkali metal salt, and a metal of the iron group in the presence of nitrogen and a hydrocarbon gas or vapor, and then recovering the resulting titaniumnitrogen compound.

' Signed at Los Angeles, day of May 1920..

FOORD VON BICHOWSKY. JOHN F. HARTHAN.

\Vitnesses:

Gnonen H. HILES, L. BELLE WEAVER.

California this 24 

